A modified method of separating Tl(I) and Tl(III) in aqueous samples using solid phase extraction

(2018) 12:132
Xiao et al. Chemistry Central Journal
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Chemistry Central Journal
Open Access

METHODOLOGY ARTICLE

A modified method of separating Tl(I)
and Tl(III) in aqueous samples using solid phase
extraction
Qingxiang Xiao1,3, Atta Rasool1,3, Tangfu Xiao2* and Philippe C. Baveye4

Abstract 
In spite of the development of new measurement techniques in recent years, the rapid and accurate speciation
of thallium in environmental aqueous samples remains a challenge. In this context, a novel method of solid phase
extraction (SPE), involving the anion exchange resin AG1-X8, is proposed to separate Tl(I) and Tl(III). In the presence
of diethylene triamine pentacetate acid (DTPA), Tl(III) and Tl(I) can be separated by selective adsorption of Tl(III)-DTPA
onto the resin, Tl(III) is then eluted by a solution of HCl with ­SO2. The validity of this method was confirmed by assays
of standard solutions of Tl(I) and Tl(III). The proposed method is shown to have an outstanding performance even in
solutions with a high ratio of Tl(I)/Tl(III), and can be applied to aqueous samples with a high concentration of other
electrolytes, which could interfere with the measurement. Portable equipment and reagents make it possible to use
the proposed method routinely in the field.
Keywords:  Thallium (III), Speciation, SPE, AG1-X8
Introduction
Thallium (Tl), a toxic trace metal and one of the USEPA’s
priority metal pollutants [1]. Although the abundance
of Tl is low in the Earth’s crust (generally < 1  mg/kg), Tl
contamination is increasing worldwide due to metal
mining/smelting activities as Tl is abundant in many
hydrothermal sulfide deposits [2]. Serious Tl pollution

has been reported in many environmental matrices collected from the mining areas [3–5]. Thallium concentrations in uncontaminated waters are usually low, generally
below < 1–2 μg/L [2]. However, at sites that are influenced
by mining activities, high levels of Tl in waters have been
reported [6–18].
In nature, Tl mainly exists in two oxidation states,
Tl(I) and Tl(III) [19, 20]. The different chemical forms
have marked different toxicities, mobilities, and biological activities. For example, Tl(III) is about 50,000 times

*Correspondence:
2
Key Laboratory for Water Quality and Conservation of the Pearl
River Delta, Ministry of Education, School of Environmental Science
and Engineering, Guangzhou University, Guangzhou 510006, China
Full list of author information is available at the end of the article

more toxic than Tl(I) to alga Chlorella as the free ion
[21]. Therefore, it is important to determine which form
of Tl is present. In recent years this has led to a significant effort to develop methods for the speciation of Tl in
environmental samples [19]. The main analytical methods used to separate and pre-concentrate Tl species
include solid phase extraction [22–31] and liquid chromatography [6, 19, 32–37]. Different chromatographic
techniques, such as cation exchange [6, 33, 38], anion
exchange [32, 33, 36, 37], size-exclusion chromatography (SEC) [33], and reversed phase-chromatography
[35] have been used to measure the redox state of Tl(I)
and Tl(III) in natural samples, with the use of inductively
coupled plasma mass spectrometry (ICP-MS) as the
mass selective detector. The chromatographic techniques
have the advantage of automatic operation, good sensitivity and separation efficiency, however, the rigorous
experimental conditions required have deterred many
researchers. Moreover, as Tl(III) is usually at trace levels it must be pre-concentrated prior to measurement,
making the chromatographic technique difficult. In this

regard, solid phase extraction (SPE) can separate and preconcentrate Tl(III), making the technique attractive for

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Xiao et al. Chemistry Central Journal

(2018) 12:132

in field preservation or measurement [25]. Samples prepared by SPE can be preserved for a long time prior to
analysis. The portable nature of the experimental equipment required for SPE make it a good candidate for Tl
speciation measurement in the field.
Speciation computational studies of the speciation of
Tl have provided some insights into the redox state of Tl
in natural waters. According to these computation studies, approximately 10% of Tl(I) in water can be present as
a ­TlSO4− complex when S
­ O4− is increased to 1
­ 0−2 mol/L
[39]. Tl(III) in water is likely to precipitate as Tl(OH)3 at
pH < 7 (Ksp25  °C = 1.68 × 10−44), whereas Tl(OH)+
2 and
Tl(OH)−
are
likely
to
form

at
even
lower
pH
of
2
[6,
32].
2
The most interesting prediction of speciation computations is that reduction of Tl(III) to Tl(I) is spontaneous
due to a high reduction potential (+ 1.26 V), unless stable
complexes are formed, such as ­TlCl4− (logK = 18), Tl(III)EDTA (logK = 22.5), Tl(III)-DTPA (logK = 46), or Tl(III)DDTC will precipitate [22]. Therefore, the addition of a
complexing agent is necessary to preserve Tl(III) in any
given aqueous system and prevent reduction to Tl(I).
A number of studies have used C
­ l− and DDTC as complexing agents for the determination of Tl(III) species in
water samples [20, 40, 41]. However, diethylene triamine
pentoacetic acid (DTPA) is more commonly used for Tl
speciation as DTPA has a higher stability constant than
­Cl−, and it does not precipitate like DDTC. In addition,
the Tl(III)-DTPA complexes is stable during chemical
preparation processes, and is stable for 7–10  days after
preparation even when exposed to UV radiation [42].
More importantly, Tl(I) does not form a complex with
DTPA [6]. To date, however, few studies have used DTPA
to speciation of Tl, mostly in tandem with liquid chromatography [33, 36–38], and SPE [25, 31], making it a good
candidate to modify for field measurements. The use of
alumina by some reported methods [25, 31] could pose
potential issues as it can absorb both the cation Tl(I) and
the anionic group of Tl(III)-DTPA [43], which makes

finding a stable and accessible sorbent difficult. The anion
exchange resin AG1-X8 has been used to pre-concentrate
Tl for Tl isotope measurements [44]. Batley and Florence
[20] used AG1-X8 to pre-concentrate Tl and assess the
concentrations of Tl(I) and Tl(III) in seawater. However,
it is not clear how applicable the method to non-saline
samples that differ substantially from the seawater for
which it was developed.
Thus, the objective of the research presented in this
manuscript is to combine the use of the AG1-X8 resin
for the separation of Tl(I) and Tl(III) with DTPA used
as the complexing agent. In principle, this approach
should enable the pre-concentration of trace levels of
Tl(III) and make it possible to quantitatively determine
Tl(I) and Tl(III) in wastewater in the presence of high

Page 2 of 7

concentrations of potentially interfering ions. Another
advantage of this approach is that it should be simple to
implement under field conditions, as separation of Tl(I)
and Tl(III) is performed in the field via the addition of
DTPA and separation by the SPE resin prior to measurement by ICP-MS.

Experimental
Reagents

Type 1 water (> 18.2  MΩ-cm) was used throughout the
experiment for the preparation of all reagents and standards. AG1-X8 analytical-grade anion-exchange resin was
purchased from BIO-RAD () in

the chloride form with a dry mesh size of 200–400 and
a wet bead size of 45–106  μm, and a nominal capacity
of 1.2  meq per mL of resin bed. Prior to use, the resin
was washed with solutions of NaCl, NaOH, and HCl in
sequence to remove any organic and inorganic impurities according to the following steps. (1) AG1-X8 resin
is washed with a saturated sodium chloride solution
in a mass to volume ratio of V
­ aq(NaCl)/V(resin) = 3:1
and then placed into a separating funnel. After allowing to soaking for 24 h, the solution was discharged, and
the resin was washed three times with type 1 water; (2)
a 1  mol/L sodium hydroxide solution is added to the
resin in a beaker in the same proportions as previously
­( Vaq(NaOH)/V(resin) = 3:1) and allowed to stand for 8 h,
it is then separated and washed as previously; 3) 1 mol/L
Hydrochloric acid (1  mol/L) is added in the same ratio
­( Vaq(HCl)/V(resin) = 3:1) and allowed to stand for 8  h
and washed as previously. The resin is then preserved in a
0.1 mol/L HCl solution for later use.
DTPA (analytical reagent, ≥ 99%) was purchased from
Sigma-Aldrich. The solution of DTPA (10  mmol/L) was
obtained by dissolving 3.93  g DTPA in 1  L type 1 water
(> 18.2  MΩ-cm) and heated to 373  K for approximately
20 min until dissolved. The solution was allowed to cool
to room temperature prior to use. Standard solutions of
Tl(I) and Tl(III) were prepared when needed by dissolving ­TlNO3 (Sigma-Aldrich) in 0.5  mmol/L ­HNO3 or by
dissolving Tl(NO3)3·3H2O (Sigma-Aldrich) in 10 mmol/L
DTPA +  5  mmol ­HNO3 solution and diluting to the
desired concentration with 400 mg/L. The standard solution of Tl(III) obtained from Tl(NO3)3·3H2O was subsequently oxidized via the following procedure. (1) 0.5 mL
of saturated bromine water was added to 10  mL of the
Tl(III) solution and stirred for 15 min with a glass rod. (2)

10  mL of a 10  mmol/L DTPA solution was then added,
and the solution was stirred for 15 min, then heating for
a further 30  min until colorless, the volume is adjusted
to 20  mL, and the solution was placed into the dark for
further use. Saturated bromine water was prepared when
needed by adding 1  mL bromine (99.99% metals basis)


Xiao et al. Chemistry Central Journal

(2018) 12:132

to 20 mL water. The SPE eluent containing 5–6% S
­ O2 in
0.1  M HCl (w/w; hereafter abbreviated as 0.1  M HCl–
SO2) was prepared following the procedures outline by
Rehkämper and Halliday [45].
The solution of saturated NaCl and 1  mol/L NaOH
were prepared by dissolving 36  g NaCl (analytical reagent, ≥ 99%) and 4 g NaOH (analytical reagent, ≥ 99%) in
100 mL type 1 water, respectively. The solutions containing 0.1, 1 and 6 mol/L HCl was prepared by adding 0.83,
8.3 and 50 mL HCl (Guaranteed reagent, 36–38%) in 100,
92 and 50 mL type 1 water, respectively. The solution of
10 mol/L ­HNO3 was prepared by adding 71.4 mL H
­ NO3
(Guaranteed reagent, 65–68%) in 29 mL type 1 water. The
solutions of 1 mol/L KI, 1 mol/L sodium thiosulfate and
1  mol/L sodium citrate were prepared by dissolution of
16.6  g KI (analytical reagent, ≥ 99%), 15.8  g sodium thiosulfate (analytical reagent, ≥ 99%), and 29.4  g sodium
citrate (analytical reagent, ≥ 99%) into 100  mL flask and
diluting to the mark with type 1 water, respectively.

SPE procedure

One millilitre of AG1-X8 resin was placed into a solidphase extraction tube fitted with a filter (Sigma-Aldrich,
6 mL). After adding the resin, the tube was covered with
a second filter, and was connected to an SPE tube adapter
and syringe. Throughout the elution process, the flow
rate through the SPE was controlled at approximately
2.0 mL/min.
The SPE procedure is outlined below (Table  1). The
prepared SPE cartridges were washed with five 1 mL aliquots of type 1 water. Following the washing step water
samples prepared with DTPA was applied to the SPE at
a flow rate of 2 mL/min. The complex of Tl(III)-DTPA is
retained on the resin. Tl(I) is unretained on the SPE resin
and is eluted from the cartridge and collected for analysis. The SPE is then washed with type 1 water (5 × 2 mL
aliquots) to remove any Tl(I) and the effluent collected
and combined with the previous affluent. To elute the
Tl(III)-DTPA complex from the column 15 mL of a 0.1 M
HCl-SO2 solution were loaded on the SPE (5 × 3 mL aliquots) the eluent collected for Tl(III) analysis.

Table 1  The SPE procedure for separation of Tl(I) and Tl(III)
from environmental aqueous samples
Step

Reagent

Aim

1

5 mL-H2O

Cleaning

2

Sample

Introduce the sample (retain
Tl(III)-DTPA and leaching
Tl(I))

2A

10 mL-H2O

Elute the co-retained Tl(I)

3

15 mL-HCl + SO2

Elute the Tl(III)

Page 3 of 7

To check the retention of Tl(I) and Tl(III) on AG1-X8
resin, standard solutions of different levels were prepared
for SPE by diluting them to desired concentrations with
5 mM DTPA solution. To check the influence of pH, the
pHs of standard solutions which contain 3500  ng Tl(I)

and 3800  ng Tl(III) were adjusted by adding solutions
of nitric acid or sodium hydroxide base on a calibrated
pH meter. To check the interferences of complexing
ions, wastewater samples were pressure-filtered through
a 0.45  μm membrane filter and 100  mL of the 10  mM
DTPA solution were added to 100  mL of filtered water,
then was divided into two aliquots, one aliquot was
spiked by standard solutions of Tl(I) and Tl(III), another
without. The two aliquots were treated with the SPE procedure described above on site, the eluents from SPE
were collected and acidified for future measurement.
Chemical analysis

The pH was measured by a pH meter (METTLER
TOLEDO, FE20, Zurich, Switzerland). The Tl content
was determined by inductively coupled plasma mass
spectrometry (ICP-MS) (Agilent, 7700×, California,
USA). Recovery of Tl measured in the certified reference material (SLRS-5) was between 94.0% and 102.2%
with a relative standard deviation of less than 10%. Rh
at 500 μg/L was used as an internal standard and added
online.

Results and discussion
Retention of Tl(I) and Tl(III) on AG1‑X8 resin

When DTPA is added to natural samples containing
Tl(III) it forms an anionic group with DTPA, which Tl(I)
cannot do. This then enables the separation of Tl(I) and
Tl(III) by the anion exchange resin AG1-X8 with the
Tl(III)-DTPA complex retaining on the SPE. The results
from the recovery of standard solutions (Table  2 and

Additional file  1: Table  S1) show that almost all Tl(I) is
leached from the SPE during the loading of the cartridge
and the washing step following the loading. While all
added Tl(III) is adsorbed to the SPE resin when Tl(III)DTPA is added, and no Tl(III) is leached. The recoveries
of Tl(I) or Tl(III) were quantitative (100 ± 2% and 99 ± 1%
respectively). In real samples, generally Tl(I) is the dominant valence state, thus solutions containing 380  ng
Tl(III) and concentrations ratios of 1-, 10-, 50- and 100fold larger of Tl(I) in 10 mL samples were tested as models of natural aqueous systems. The recoveries of these
mixtures of Tl(I) and Tl(III) were satisfactory (98–106%;
Table 2 and Additional file 1: Table S1) suggests that the
SPE method is fit for the purpose of separating Tl(I) and
Tl(III) in water samples.
To elute Tl(III)-DTPA from the SPE resin, several solutions were assessed, including 6  mol/L HCl, 10  mol/L


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Page 4 of 7

Table 2  Recovery of Tl(I) and Tl(III) from samples prepared by standard solution
Tl species

Tl(I):Tl(III)
1:0 (%)

0:1 (%)

1:1 (%)

Tl(I)

100 ± 2

0.2 ± 0.1

101 ± 4

Tl(III)

0.3 ± 0.03

99 ± 1

98 ± 4

Total Tl

100 ± 2

99 ± 1

100 ± 4

10:1 (%)
103 ± 6
100 ± 0.8
102 ± 5

50:1 (%)

100:1 (%)

99 ± 2

97 ± 6

106 ± 2

109 ± 1

99 ± 1

97 ± 6

The samples, all of 10 mL volume, contain 350 ng Tl(I) (1:0 column), 380 ng Tl(III) (0:1 column), or solutions containing 380 ng Tl(III) and concentrations ratios of 1-, 10-,
50- and 100-fold larger of Tl(I) in 10 mL samples were tested. The results are presented as mean values ± SD (n ≥ 3)

Table 3 The recovery of  Tl(I) and  Tl(III) from  samples
at different pH
pH

Tl(I), %

Tl(III), %

pH = 1

102 ± 1

100 ± 6

101 ± 3

pH = 2

98 ± 6

104 ± 6

101 ± 6

pH = 3

97 ± 3

101 ± 2

pH = 4

95 ± 4

98 ± 0.8
99 ± 0.3

Total Tl, %

99 ± 2
97 ± 2

pH = 5

97 ± 3

pH = 6

97 ± 2

101 ± 2

99 ± 2

98 ± 2

pH = 7

97 ± 0.2

103 ± 3

100 ± 2

The samples at pH from 1 to 7 contain 3500 ng Tl(I) and 3800 ng Tl(III) in 3–8 mL.
The results are presented as mean values ± SD (n ≥ 3)

­HNO3, 1 mol/L KI, 1 mol/L sodium thiosulfate, 1 mol/L
sodium citrate, and 0.1  M HCl-SO2 solution. Among
them, 6  mol/L HCl and 10  mol/L ­HNO3 did not elute
any Tl(III) from the resin, while KI and sodium thiosulfate could precipitate with ­HNO3. The solution of sodium
citrate did elute Tl(III)-DTPA from the SPE but lead to

difficulties later on when quantifying Tl(III) by ICP-MS.
Therefore, the solution of 0.1 M HCl–SO2 was selected as
the eluent.
Influence of pH

As pH could influence the hydrolysis of DTPA in water
[33, 46], and further adsorption onto the resin, it was
essential to establish if pH has an overall effect on the
interaction of the Tl(III) and the resin. The results indicate that solutions containing Tl(I) and Tl(III) at various
pH’s (from 1 to 7), showed near quantitative recoveries
of Tl (95–103%; Table 3 and Additional file 1: Table S2).
There was no significant differences in recoveries under
different pH conditions according to the Duncan’s new
multiple range test base on the SPSS software, therefore,
no optimal pH can be established.
Standard solution of Tl(III)

As Tl(III) can be easily reduced to Tl(I) under natural
conditions, assessing the stability of the Tl(III)-DTPA
complex is essential [42]. The preparation process of
the standards may be compromised as Tl(III) could be

reduced to Tl(I) even in the presence of DTPA. Without oxidation, about 34% of Tl(III) was reduced to Tl(I)
in this experiment. Therefore, saturated bromine water
was applied for oxidation of Tl(I). Oxidation of Tl(I) was
also carried out independently to check the function of
DTPA. Saturated bromine water (0.4 mL) was added to a
solution containing 4000 ng Tl(I) in 10 mL. The solution
was stirred for 15  min with a glass rod and then 10  mL
of 10 mmol/L DTPA was added. The solution was stirred

for a further 15 min (the color of the solution is yellow),
and heated (333 K) until it became colorless and allowed
to cool. The resulting solution was then dilution to a
total volume of 20  mL and assessed by the SPE method
described above. The results showed that when preparing the standard in this way, Tl(I) was fully oxidised to
Tl(III), the same results are obtained when replacing
DTPA solution with solid DTPA. However, the Tl(III)
oxidized by saturated bromine water was quickly reduced
to Tl(I) without the addition of DTPA. It should be noted
that, although NaOH is frequently used to prepare DTPA
solutions [25], DTPA with NaOH is not recommended to
treat aqueous samples, as we observed that the addition
of NaOH interferes with the oxidation process of Tl(I) to
Tl(III) (data not shown).
Interferences

Natural aqueous samples with elevated Tl are usually
characterized by high concentrations of other cations
and anions as well, and these other ions could in principle interfere with the analysis. The potential influence of
cations on the absorption capacity of the anion exchange
resin is limited, however, anions could influence it
directly, as they would compete for adsorption onto the
anionic group of Tl(III)-DTPA. Thus, two aqueous samples with high concentrations of cations and anions were
checked by spiking with standard Tl solutions. The major
ions of two aqueous samples are listed in Table 4. Sample
A is a leachate sample from Pb–Zn smelting slags in Yunnan Province, China. Sample B is an acid mine drainage
(AMD) water sample from Lanmuchang Tl deposits, in
Guizhou Province, China. A 1-mL aliquot of the standard
Tl solution containing 40 ng of Tl(I) and 40 ng of Tl(III)
was added to 1 mL of the two samples, respectively. The

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Table 4  Major ions in samples A and B (mg/L)
Sample

Mn

Zn

Cd

Tl

Pb

A

2445 ± 9

5277 ± 13

52 ± 3

0.14 ± 0.02

0.9 ± 0.1

B

0.95 ± 0.07

< 0.1

0.07 ± 0.002

< 0.1

0.4 ± 0.04

Fe
73 ± 6
116 ± 10

Cl−
105 ± 4
0.87 ± 0.03

SO42−
21,681 ± 30
1283 ± 18

The results are presented as mean values ± SD (n ≥ 3)

average recoveries of Tl(I) and Tl(III) remain identical, at

100 ± 1% (n ≥ 3) and 101 ± 3% (n ≥ 3), respectively, in the
two cases, to what had been found in uncontaminated
waters.
Sample volume

The nominal capacity of AG1-X8 resin is 1.2 meq per mL
of resin bed. In theory, 1-mL of AG1-X8 resin can sorb
only 1.2/X mmol (X: valence of anion) of anions. The following formula can be used to estimate the volume of
sample that can be separated by 1 mL resin:

V = 1.2/ ax + by + cz + · · ·
where the volume of the sample is expressed in V (L),
and the concentration of the major anions and the corresponding valence states are expressed by a, b, c, etc.
(mmol/L) and x, y, z, etc., respectively. Therefore, to
determine the amount of resin needed and the maximum volume of sample that applied to the resin, we need
to know the approximate content of the main anions
before conducting the experiment. If the total amount
of anions in a sample exceeds the capacity of the resin,
the adsorbed Tl(III) may be washed off, resulting in a low
recovery of Tl(III). For example, the maximum volume of
our sample A (Table 4) for 1 mL resin could be estimated
by using the concentration of ­SO42− and ­Cl− instead of all
anions. The maximum volume (V) of sample A for 1 mL
resin should be less than 2.6 mL according to the following calculation: V 
= 1.2/((21,681/96) × 2+(105/35) × 1) 
= 0.0026 L. Of course, the complex computational process can be replaced by a spike experiment with the same
volume of resin and water sample. If the recovery of the
spike experiment is quantitative, it establishes that the
volume of the sample does not exceed the binding capacity of the resin.
Suggestion of practical application

The method described has demonstrated an outstanding
performance in wastewater samples analyzed from AMD
and smelting slags by spiking experiment conducted with
Tl(I) and Tl(III) standards as mentioned above. DTPA
is necessary for preservation of Tl(III) and determination of Tl speciation. For natural waters, it was found
that 0.1 g DTPA per 50 mL samples was required to preserve Tl(III), a similar pretreatment process of water as

suggested by Campanella [6]. And it is better to perform
spiking experiments with standard solutions of Tl(I) and
Tl(III) to check whether interfering compounds of the
water samples have an adverse effect on the separation
experiment.
The limit of detection (LOD) for Tl species analysis was
calculated as 3-times the standard deviation of Tl concentration in the blank samples (10 mL) (mean + 3 × SD,
n = 10), and was established as 5  ng/L for Tl(I) and
16  ng/L for Tl(III). DTPA is the only reliable agent for
pre-treatment of Tl in water sample, therefore, the present method is less destructive but sufficiently sensitive
compare to previous Tl-speciation methods. This method
can also separate and pre-concentration of Tl(III) from
the dominate Tl(I) and other interfering compounds.
Compared to previous SPE methods [25], the resin AG1X8 is more stable and reliable than alumina.

Conclusions
The rapid and accurate testing of thallium (Tl) speciation in water samples is important to human and environmental health. In this study, we developed a modified
method of solid phase extraction (SPE), using the anion
exchange resin AG1-X8, to measure Tl(I) and Tl(III)
species in water samples. With the use of diethylene
triamine pentacetate acid (DTPA), Tl(III) and Tl(I) species were separated by the formation of Tl(III)-DTPA
complex which is selectively adsorbed onto the AG1-X8

resin. The Tl(III)-DTPA can be effectively eluted from
the resin with a solution of HCl with ­SO2. The validity of
this method was confirmed by the high Tl recoveries of
Tl(I) and Tl(III). The present method was demonstrated
to have an outstanding performance not only for waters
with high Tl(I)/Tl(III) ratios, but also for waters with high
levels of interfering compounds, such as ­SO42−, ­Cl−, Zn,
Pb, Mn, Fe, and so on. Our method, which can be also
used to pre-concentrate Tl(III) and can be performed
under wide pH ranges, shows some advantages compared
to the commonly used chromatographic method.


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Additional file
Additional file 1: Table S1. The measured Tl(I) and Tl(III) from standard
solutions at different Tl(I)/Tl(III) ratios. Table S2. The measured Tl(I) and
Tl(III) from standard solutions at different pH.
Abbreviations
SPE: solid phase extraction; DTPA: diethylene triamine pentoacetic acid; ICPMS: inductively coupled plasma mass spectrometry; AMD: acid mine drainage.
Authors’ contributions
TX and QX participated in designing the method which presented in the
manuscript. AR and QX carried out the experimental and the ICP-MS analysis.
QX wrote most of the manuscript. TX and PCB provided the overall concept
and critically edited for the manuscript. All authors read and approved the
final manuscript.
Author details

1
 State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550081, China. 2 Key Laboratory
for Water Quality and Conservation of the Pearl River Delta, Ministry of Education, School of Environmental Science and Engineering, Guangzhou University, Guangzhou 510006, China. 3 University of Chinese Academy of Sciences,
Beijing 100049, China. 4 UMR Ecosys, Université Paris‑Saclay, AgroParisTech,
Avenue Lucien Brétignières, 78850 Thiverval‑Grignon, France.
Acknowledgements
The two anonymous reviewers are acknowledged for their critical comments
and suggestions which have considerably improved the manuscript. Thanks
also go to Prof. Simon Foster from Institute for Applied Ecology, University of
Canberra, Australia for final text edition.
Competing interests
The authors declare that they have no competing interests.
Availability of data and materials
The datasets supporting the conclusions of this article are include within the
article and its additional file.
Consent for publication
All the authors have approved to submit the manuscript.
Ethics approval and consent to participate
Not applicable.
Funding
This work was funded the National Natural Science Foundation of China
(41830753, U1612442, 41473124, 41673138).

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Received: 14 April 2018 Accepted: 27 November 2018

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